CN1147521C - Process for preparing polyethylene terephthalate - Google Patents
Process for preparing polyethylene terephthalateInfo
- Publication number
- CN1147521C CN1147521C CNB971182884A CN97118288A CN1147521C CN 1147521 C CN1147521 C CN 1147521C CN B971182884 A CNB971182884 A CN B971182884A CN 97118288 A CN97118288 A CN 97118288A CN 1147521 C CN1147521 C CN 1147521C
- Authority
- CN
- China
- Prior art keywords
- polyethylene terephthalate
- esterifier
- pet
- compound
- terephthalic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000139 polyethylene terephthalate Polymers 0.000 title claims abstract description 110
- 239000005020 polyethylene terephthalate Substances 0.000 title claims abstract description 109
- -1 polyethylene terephthalate Polymers 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 122
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 82
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000007791 liquid phase Substances 0.000 claims abstract description 42
- 238000005886 esterification reaction Methods 0.000 claims abstract description 36
- 230000032050 esterification Effects 0.000 claims abstract description 35
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 claims abstract description 33
- 150000001463 antimony compounds Chemical class 0.000 claims abstract description 33
- 239000002002 slurry Substances 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 229920000728 polyester Polymers 0.000 claims abstract description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000001869 cobalt compounds Chemical class 0.000 claims description 9
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 150000002681 magnesium compounds Chemical class 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- 150000002697 manganese compounds Chemical class 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 31
- 238000000465 moulding Methods 0.000 description 26
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 19
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- 239000007795 chemical reaction product Substances 0.000 description 18
- 239000003595 mist Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- 235000011007 phosphoric acid Nutrition 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 235000015067 sauces Nutrition 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 240000007154 Coffea arabica Species 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 235000015429 Mirabilis expansa Nutrition 0.000 description 1
- 244000294411 Mirabilis expansa Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 235000006468 Thea sinensis Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 235000020279 black tea Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 235000009569 green tea Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229960002337 magnesium chloride Drugs 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 239000004337 magnesium citrate Substances 0.000 description 1
- 229960005336 magnesium citrate Drugs 0.000 description 1
- 235000002538 magnesium citrate Nutrition 0.000 description 1
- OVGXLJDWSLQDRT-UHFFFAOYSA-L magnesium lactate Chemical compound [Mg+2].CC(O)C([O-])=O.CC(O)C([O-])=O OVGXLJDWSLQDRT-UHFFFAOYSA-L 0.000 description 1
- 239000000626 magnesium lactate Substances 0.000 description 1
- 235000015229 magnesium lactate Nutrition 0.000 description 1
- 229960004658 magnesium lactate Drugs 0.000 description 1
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 235000013536 miso Nutrition 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- ZFACJPAPCXRZMQ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O.OC(=O)C1=CC=CC=C1C(O)=O ZFACJPAPCXRZMQ-UHFFFAOYSA-N 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000019991 rice wine Nutrition 0.000 description 1
- 235000020083 shōchū Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/785—Preparation processes characterised by the apparatus used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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Abstract
Disclosed is a method for preparing polyethylene terephthalate, the polyester preparation apparatus comprises an esterification reactor consisting of a plurality of continuous esterification reactors, a liquid phase polycondensation reactor and an optional solid phase polycondensation reactor, the method comprises the following steps: the slurry containing terephthalic acid, ethylene glycol and antimony compounds is fed to a first esterification reactor and a phosphorus compound and, optionally, at least one compound selected from the group consisting of cobalt, magnesium and manganese compounds is fed to a second or subsequent esterification reactor. Using this process, polyethylene terephthalate having good color and excellent transparency and suitable for bottle making can be prepared.
Description
The present invention relates to a kind of method for preparing polyethylene terephthalate, relate in particular to the method that preparation has the polyethylene terephthalate of good color and good transparency.
Polyethylene terephthalate has been widely used in the production of for example fiber, film, bottle and industrial material.Especially recently a large amount of polyethylene terephthalate bottles (PET bottle) have been used for replacing vial or metal tin, and therefore the amount of the polyethylene terephthalate of bottle usefulness rises.Bottle needs good extensibility, good transparency, good color and high voltage performance with polyethylene terephthalate.
Up to now, propose the multiple method for preparing polyethylene terephthalate, proposed the various methods that in the preparation of polyethylene terephthalate, add catalyzer in addition.
For example, be disclosed in the Japanese patent application publication No. 91993/1976 and add ANTIMONY TRIOXIDE SB 203 99.8 PCT and phosphorous acid in the esterif iotacation step simultaneously.Yet, in esterif iotacation step, adding ANTIMONY TRIOXIDE SB 203 99.8 PCT and phosphorous acid simultaneously, antimony metal can precipitate and the bottle color variation that causes the polyethylene terephthalate with gained to make, and transparency descends.
Japanese patent application publication No. 11214/1986 discloses a kind of antimony compounds that is dissolved in ethylene glycol is added respectively in the different esterification devices with phosphotriester.Yet this method needs an additional unit that antimony compounds is dissolved in ethylene glycol.And because ethylene glycol must at high temperature heat and dissolve antimony compounds, this section heat-processed may cause the increase of glycol ether amount, or makes the color variation of gained polyethylene terephthalate.
As mentioned above, the method that proposes usually always is not applicable to the preparation of bottle with polyethylene terephthalate.
The present invention makes in these cases.The purpose of this invention is to provide the method that a kind of preparation has good color and good transparency and is applicable to the polyethylene terephthalate of system bottle.
The invention provides a kind of method for preparing polyethylene terephthalate, this method is carried out in the polyester manufacture device, this device comprises an esterifier of being made up of a plurality of continuous esterification devices, and a liquid phase polycondensation reaction device is characterized in that aforesaid method may further comprise the steps:
The slurries that will contain terephthalic acid, ethylene glycol and antimony compounds add in first esterifier; And
With a kind of phosphorus compound, and optional, be selected from least a compound in cobalt compound, magnesium compound and the manganic compound add second or later esterifier in.
Among the present invention, ANTIMONY TRIOXIDE SB 203 99.8 PCT can be used as antimony compounds.In terephthalic acid, the blending ratio of antimony compounds is preferably in the scope of 150-400ppm.
The slurries that contain terephthalic acid, ethylene glycol and antimony compounds are preferably under 0-50 ℃ the temperature and prepare.
Temperature of reaction in first esterifier is preferably in 240 to 270 ℃ the scope.
Phosphorus compound, cobalt compound, magnesium compound and manganic compound are can their aqueous solution or the form of ethylene glycol solution reinforced.
Except terephthalic acid, m-phthalic acid can be used as the dicarboxylic acid component, and its content is 1-3% (mole), in all dicarboxylic acid components.
Fig. 1 is the schema that explanation the present invention prepares an embodiment of polyethylene terephthalate method.
1: mixing tank
2: esterifier
3: the liquid phase polycondensation reaction device
4: extrusion machine
5: the solid state polycondensation device
Describe the method that the present invention prepares polyethylene terephthalate below in detail.
Among the present invention, the polyester reaction unit that is used to prepare polyethylene terephthalate comprises the esterifier of being made up of a plurality of continuous esterification devices, liquid phase polycondensation reaction device, and optional solid state polycondensation device.
According to the present invention, the slurries that contain terephthalic acid, ethylene glycol and antimony compounds catalyzer are added first esterifier.
Can contain the slurries of terephthalic acid, ethylene glycol and antimony compounds with batch process or continuous processing preparation, equipment therefor for example is furnished with the vertical or horizontal mixing tank of helical-ribbon type agitating vane.In slurries, terephthalic acid and antimony compounds disperse or are suspended in the ethylene glycol.
The temperature that terephthalic acid, ethylene glycol and antimony compounds are mixed with slurries is generally 0-50 ℃, preferably 10-40 ℃.
In the said temperature scope, antimony compounds is dissolved in the ethylene glycol hardly, but terephthalic acid and antimony compounds can disperse or be suspended in to form slurries in the ethylene glycol.And, the rotten of ethylene glycol can be taken place hardly, and reduced the amount of the glycol ether that forms.
In the slurries, in 1 mole of terephthalic acid, glycol content is generally the 1.02-2.0 mole, 1.03-1.5 mole preferably, and the content of antimony compounds is generally 50-500ppm, preferably 150-400ppm (in metallic antimony).
The example of antimony compounds comprises ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony acetate and butter of antimony.The median size of antimony compounds generally is about the 5-20 order preferably, better is about 10 orders.
Among the present invention, prepare polyethylene terephthalate as raw material with terephthalic acid and ethylene glycol.But also can use other dicarboxylic acid and/or other dibasic alcohol in addition, its consumption must not surpass 20% (mole).
The example of other dicarboxylic acid that can be used for copolycondensation except that terephthalic acid comprises aromatic dicarboxylic acid, as phthalic acid (phthalic acid), m-phthalic acid, naphthalene dicarboxylic acids, diphenyl dicarboxylic acid and biphenoxyl ethane dicarboxylic acid; Aliphatic dicarboxylic acid is as hexanodioic acid, sebacic acid, nonane diacid and decane dicarboxylic acid; The alicyclic ring dicarboxylic acid is as cyclohexane dicarboxylic acid.
The example of other dibasic alcohol that is used for copolycondensation except that ethylene glycol comprises aliphatic diol, as 1, and ammediol, 1,2-propylene glycol, 1,4-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol and 1,12-dodecanediol; The alicyclic ring dibasic alcohol is as cyclohexanedimethanol; And aromatic dihydroxy compound, as bisphenols, quinhydrones and 2,2-two (4-beta-hydroxy ethoxyl phenenyl) propane.
Among the present invention, preferably, except terephthalic acid, as the dicarboxylic acid component, its consumption is 1-3% (mole), in all dicarboxylic acid components with m-phthalic acid.
According to the present invention, a kind of phosphorus compound, and optional, be selected from least a compound in cobalt compound, magnesium compound and the manganic compound add second or later esterifier in.
The example of phosphorus compound comprises phosphoric acid ester, as trimethyl phosphite 99, triethyl phosphate, TRI N BUTYL PHOSPHATE, trioctyl phosphate, triphenylphosphate and Tritolyl Phosphate; Phosphorous acid ester is as triphenyl phosphite, tricresyl phosphite (dodecane) ester and tricresyl phosphite (nonyl benzene) ester; Phosphate ester acid is as acid methyl orthophosphoric acid, acidic isopropyl phosphate, acid butyl phosphate, dibutyl phosphate, monobutyl phosphate and dioctylphosphoric acid ester; Phosphoric acid; And Tripyrophosphoric acid.By phosphorus compound is added esterifier, can improve the color and the thermostability of the polyethylene terephthalate of gained.
The example of cobalt compound comprises cobalt chloride, rose vitriol, cobaltous hydroxide, Xiao Suangu, cobalt oxalate, cobaltous formate, cobaltous acetate, acetylacetone cobalt and cobaltous benzoate.By in esterifier, adding cobalt compound, can quicken esterification.
The example of manganic compound comprises manganous acetate, manganese acetylacetonate, manganous sulfate, manganous carbonate and manganous nitrate.By in esterifier, adding manganic compound, can quicken esterification.
The example of magnesium compound comprises sal epsom, magnesium nitrate, magnesium acetate, magnesium chloride, magnesiumcarbonate, magnesium citrate, magnesium lactate and magnesium oxalate.By in esterifier, adding magnesium compound, can quicken esterification.
Above compound generally adds with its aqueous solution or ethylene glycol solution form.When they add fashionablely with aqueous solution form, the water yield is preferably the least possible.
The consumption of phosphorus compound in 1 mole of terephthalic acid, is generally 5-200ppm, preferably 10-100ppm (in phosphorus atom).
The consumption of cobalt compound in 1 mole of terephthalic acid, is generally 5-200ppm, preferably 10-60ppm (in cobalt metal).
The consumption of manganic compound in 1 mole of terephthalic acid, is generally 10-200ppm, preferably 20-100ppm (in manganese metal).
The consumption of magnesium compound in 1 mole of terephthalic acid, is generally 5-200ppm, preferably 15-50ppm (in MAGNESIUM METAL).
Can with above compound simultaneously or one after the other add second or later esterifier in, preferably add in second esterifier.
In the present invention, antimony compounds adds in first esterifier with the slurries form with terephthalic acid and ethylene glycol as the catalyzer of polycondensation, and phosphorus compound etc. add second or later esterifier in, metallic antimony can precipitate hardly like this.These are different with the prior art situation that antimony compounds, phosphorus compound etc. is added simultaneously esterifier.Therefore, can obtain having the good color and the polyethylene terephthalate of transparency.
Esterification is carried out under ethylene glycol refluxes, and water or alcohol that reaction simultaneously forms are removed from system by separation column.
Esterification can carried out under the following condition: in the first step esterification, temperature is generally 240-270 ℃, and preferably 245-265 ℃, pressure is generally 0.2-3kg/cm
2-G, preferably 0.5-2kg/cm
2-G; In the end in the esterification in a step, temperature is generally 250-280 ℃, and preferably 255-275 ℃, pressure is generally 0-1.5kg/cm
2-G, preferably 0-1.3kg/cm
2-G.
When esterification was carried out with two steps, the first and second step esterification conditions were respectively in the condition and range of above-mentioned first and final step.When esterification with three steps or when more multistep is carried out, second the esterification condition except that the first step to final step be above-mentioned first and the condition of final step between select.
For example, when esterification was carried out with three steps, the second step esterification is carried out under the following conditions: temperature was generally 245-275 ℃, and preferably 250-270 ℃, pressure is generally 0-2kg/cm
2-G, preferably 0.2-1.5kg/cm
2-G.
For each the step esterification transformation efficiency do not have concrete restriction, but preferably transformation efficiency along with each step increases progressively gradually.The transformation efficiency of final step esterification generally reaches and is not less than 90%, preferably is not less than 93%.
In esterification, can add a small amount of basic cpd, for example, and tertiary amine, as Trimethylamine 99, tri-n-butylamine and benzyl dimethyl amine; Quaternary ammonium compound is as tetraethylammonium hydroxide, hydroxide tetra-n-butyl ammonium and benzyltrimethyl ammonium hydroxide; Also have Quilonum Retard, yellow soda ash, salt of wormwood and sodium acetate.It is preferable adding basic cpd in esterification, because the terephthalic acid two in the polyethylene terephthalate main chain (the inferior second of oxygen) the unitary ratio of ester (dioxyethylene terephthalate) component can remain on lower level.
The number-average molecular weight of the esterification products that obtains by above-mentioned step of esterification (low polycondensate) is generally 500 to 5,000.
Then, the above esterification products that obtains is added the liquid phase polycondensation reaction device with antimony compounds, phosphorus compound etc., wherein antimony compounds, phosphorus compound etc. add esterifier with the ethylene glycol solution state.
Liquid phase polycondensation reaction is following to carry out: in the presence of polycondensation catalyst, and decompression and with the temperature heating systems of the polyethylene terephthalate fusing point that is not less than gained, the dibasic alcohol that reaction is generated distills away from system simultaneously.
Liquid phase polycondensation reaction can be undertaken by a step or multistep.When liquid phase polycondensation reaction carried out with multistep, the temperature of the first step polycondensation was generally 250-290 ℃, and preferably 260-280 ℃, pressure is the 500-20 torr, preferably the 200-30 torr; The temperature of final step polycondensation is 265-300 ℃, and preferably 270-295 ℃, pressure is the 10-0.1 torr, is the 5-0.1 torr preferably, better is the 2-0.1 torr.
When liquid phase polycondensation reaction carried out with two steps, the first and second one-step polycondensation reaction conditionss were respectively in the condition and range of above-mentioned first and final step.When liquid phase polycondensation reaction with three steps or when more multistep is carried out, second the polycondensation condition except that the first step to final step be above-mentioned first and the condition of final step between select.
For example, when liquid phase polycondensation reaction carried out with three steps, the reaction of second one-step polycondensation is carried out under the following conditions: temperature was generally 260-295 ℃, and preferably 270-285 ℃, pressure is generally the 50-2 torr, preferably the 40-5 torr.
Limiting viscosity (IV) for the polyethylene terephthalate that makes with liquid phase polycondensation reaction does not have concrete restriction.But best properties viscosity is to increase progressively gradually along with each step.The limiting viscosity of the polyethylene terephthalate that the final step polycondensation obtains (IV) is generally 0.35-0.80dl/g, is 0.45-0.75dl/g preferably, and that best is 0.55-0.75dl/g.
The viscosity calculations of solution obtained when limiting viscosity can be from measure 25 ℃, and this solution is 1.2 gram polyethylene terephthalates to be dissolved in 15 cubic centimetres the orthomonochlorphenol by the limit heating edge, and cooling obtains then.
As mentioned above, the polyethylene terephthalate that obtains by liquid phase polycondensation reaction can contain from the component unit of other dicarboxylic acid except that terephthalic acid with from the component unit of other dibasic alcohol except that ethylene glycol, and its content is no more than 20% (mole).Goodish situation is to be 1-3% (mole) from the unitary content of the component of m-phthalic acid, in all dicarboxylic acid units.The unitary polyethylene terephthalate of m-phthalic acid that contains above-mentioned content has excellent color and transparency.
In the present invention, preferably the unitary content of terephthalic acid ethylene glycol component shown in the following formula (I) is in the scope of 95.0-99.0%, and the terephthalic acid two shown in the following formula (U) (the inferior second of oxygen) the unitary content of ester component is in the scope of 1.0-5.0%:
The polyethylene terephthalate that obtains in the final step liquid phase polycondensation reaction device generally is molded into granular (section) with melt extruding the method for forming.Require the mean diameter of granular polyethylene terephthalate to be generally 2.0-5.0mm, preferably 2.2-4.0mm.
Then, the granular polyethylene terephthalate that obtains by liquid phase polycondensation reaction carries out solid state polycondensation, and this can select.
The granular polyethylene terephthalate that adds the solid state polycondensation device can carry out pre-crystallization.Pre-crystallization is undertaken by heating granular polyethylene terephthalate, and Heating temperature is lower than the temperature of solid state polycondensation.Specifically, granular polyethylene terephthalate heats under drying regime, and Heating temperature is generally 120-200 ℃, and preferably 130-180 ℃, be 1 minute to 4 hours heat-up time; Perhaps heat under the atmosphere of the air of the rare gas element of water vapor, moisture vapor or moisture vapor, Heating temperature is generally 120-200 ℃, is no less than 1 minute heat-up time.
Solid state polycondensation comprises a step at least, carries out under the following conditions: temperature is generally 190-230 ℃, preferably 195-225 ℃; Pressure is generally 1kg/cm
2-G to 10 torr, preferably barometric point to 100 torr; Atmosphere is rare gas element, as nitrogen, argon gas or carbon dioxide.In these rare gas elementes, nitrogen preferably.
The limiting viscosity of the polyethylene terephthalate that obtains by solid state polycondensation generally is not less than 0.50dl/g, is not less than 0.54dl/g preferably, better is not less than 0.70dl/g, the best 0.72dl/g that is not less than; Its density generally is not less than 1.37g/cm
3, be not less than 1.38g/cm preferably
3, better be not less than 1.39g/cm
3
Require the content of the oligopolymer (the unitary cyclic trimerization thing of the terephthalic acid ethylene glycol component of following formula (I)) of polyethylene terephthalate to be no more than 0.6% (weight), be no more than 0.5% (weight) preferably, better be no more than 0.45% (weight), best 0.4% (weight) that is no more than.
Next, with reference to figure 1 the present invention is described in further detail.Fig. 1 prepares the schema of an embodiment of the method for polyethylene terephthalate for the present invention.In this embodiment, esterifier 2 is made up of first esterifier 21, second esterifier 22 and the 3rd esterifier 23; Liquid phase polycondensation reaction device 3 is made up of the first liquid phase polycondensation reaction device 31 and the second liquid phase polycondensation reaction device 32.
Terephthalic acid, ethylene glycol and antimony compounds catalyzer add in the mixing tank 1 by feed- pipe 11,12 and 13 respectively and prepare slurries.In slurries, terephthalic acid and antimony compounds generally disperse and are suspended in the ethylene glycol.
Slurries are sent in first esterifier 21 by fresh feed pump 17.Then, the reaction product in first esterifier 21 is admitted in second esterifier 22, and the reaction product in second esterifier 22 is admitted in the 3rd esterifier 23 again.In each reactor of first to the 3rd esterifier 21 to 23, carry out esterification until reaching desired esterification transformation efficiency.With phosphorus compound, and optional cobalt compound etc. adds in second esterifier 22 by feed-pipe 14.The water that esterification generates is separated from ethylene glycol by separation column 15.
The above-mentioned esterification reaction product that obtains is extracted out from the 3rd esterifier 23 continuously by pump 18, sends into the first liquid phase polycondensation reaction device 31 then.Reaction product in the first liquid phase polycondensation reaction device 31 is admitted in the second liquid phase polycondensation reaction device 32.In each reactor of the first and second liquid phase polycondensation reaction devices 31 and 32, carry out liquid phase polycondensation reaction until reaching desired limiting viscosity.Remove by separator 16 by the dibasic alcohol that liquid phase polycondensation reaction generates.
The polyethylene terephthalate that is obtained by the second liquid phase polycondensation reaction device 32 is admitted to extrusion machine 4, is molded into granular.
Granular polyethylene terephthalate is admitted to solid state polycondensation device 5 and carries out solid state polycondensation.
The method according to this invention is mixed with terephthalic acid and ethylene glycol as the antimony compounds of polycondensation catalyst, is present in the esterifier with slurry condition, and need not in advance antimony compounds to be dissolved in the ethylene glycol.Therefore, need not special dissolution vessel, and reduced number of steps and simplified device, make cost reduce.In addition, need not ethylene glycol is heated to high temperature or it is remained in high temperature with the dissolving antimony compounds.Therefore, the rotten of ethylene glycol can be taken place hardly, and reduce the glycol ether amount that generates.
In addition, the slurries of antimony containing compounds are added in first esterifier in a plurality of esterifiers, so just can not cause owing in condensation polymerization step, adding the contamination that foreign matter that insoluble antimony compounds causes brings and the decline of transparency.
Moreover, the first step that antimony compounds is added esterif iotacation step, and phosphorus compound is added second step of esterif iotacation step or later step, and having suppressed the precipitation of metallic antimony thus, the bottle that makes polyethylene terephthalate by gained make has good color and transparency.
Because the polyethylene terephthalate by the inventive method preparation has the transparency of good color and height, therefore it is applicable to bottle such as grape wine, rice wine and shochu, castor such as soy sauce, chile sauce (Worcester sauce) and beans sauce (miso), and beverage bottle such as soda pop, mineral water, fruit juice, green tea, coffee and black tea.
Further describe the present invention with reference to following examples, but should think that the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
The successive polycondensation reaction device is made up of the reactor and horizontal twin screw rotary (horizontal twin-screw rotary type) the 5th reactor of first to fourth container type.In this device, the polycondensation of carrying out ethylene glycol and terephthalic acid in the following manner continuously is with preparation polyethylene terephthalate (PET).
Place the reaction soln of 3,750 weight parts in first reactor in advance, this solution is in nitrogen atmosphere, in 255 ℃ and 1.7kg/cm
2-G stirs down.With highly purified terephthalic acid and ethylene glycol and ANTIMONY TRIOXIDE SB 203 99.8 PCT mixing, the preparation slurries, these slurries are added first reactor in the following manner continuously carry out the first step esterification: the high purity terephthalic acid is with per hour 1, the speed of 437 weight parts adds, ethylene glycol is with the per hour speed adding of 645 weight parts, and ANTIMONY TRIOXIDE SB 203 99.8 PCT is with the per hour speed adding of 0.57 weight part.During the first step esterification, water is with the speed of 203 weight parts per hour, and ethylene glycol is distillated with the speed of 3 weight parts per hour.It is 2.0 hours that control the first step esterification makes the mean residence time of slurries.The slurries of discharging from first reactor are sent into second reactor continuously, and this reactor remains on 260 ℃ and 0.8kg/cm
2Following and the stirring of-G.
The phosphoric acid with 85% and the homogeneous phase solution of ethylene glycol add second reactor in the following manner continuously: 85% phosphoric acid is with the per hour speed adding of 0.46 weight part, and ethylene glycol is with the per hour speed adding of 9 weight parts.Simultaneously, water and ethylene glycol respectively with the speed of 84 weight parts per hour and per hour the speed of 7 weight parts distillate continuously.Carry out the second step esterification like this, controlling the mean residence time that this reaction makes slurries is 2.0 hours.The slurries of discharging from second reactor are sent into the 3rd reactor continuously, and this reactor remains on 275 ℃ of following and stirrings with 70mmHg.
In the 3rd reactor, ethylene glycol and water respectively with the speed of 62 weight parts per hour and per hour the speed of 6 weight parts distillated continuously, to carry out the first step polycondensation, controlling the mean residence time that this polycondensation makes reaction mixture is 1.0 hours.The polycondensation product of discharging from the 3rd reactor is sent into the 4th reactor continuously, and this reactor remains on 280 ℃ of following and stirrings with 5mmHg.
In the 4th reactor, ethylene glycol and water respectively with the speed of 26 weight parts per hour and per hour the speed of 3 weight parts distillated continuously, to carry out the reaction of second one-step polycondensation, controlling the mean residence time that this polycondensation makes reaction mixture is 1.0 hours.The polycondensation product of discharging from the 4th reactor is sent into the 5th reactor (the rotary reactor of horizontal twin screw) continuously, and this reactor remains on 282-285 ℃ of following and stirring with 1.8-2.5mmHg.
In the 5th reactor, ethylene glycol and water respectively with the speed of 12 weight parts per hour and per hour the speed of 1 weight part distillated continuously, to carry out the reaction of the 3rd one-step polycondensation, controlling the mean residence time that this polycondensation makes polycondensation product is 2.5 hours.Polycondensation product is pulled straight with line material form from reactor by the polyester machine of pulling out.Then, will cool off in this line material immersion water, and use the line material to cut off, obtain cutting flaky polyethylene terephthalate (PET) with cutting machine (strand cutter).
The limiting viscosity of the PET that obtains by above-mentioned liquid phase polycondensation reaction is measured in orthomonochlorphenol in 25 ℃, be 0.58dl/g, and PET contains the glycol ether unit of 0.95% (weight).
Then, the PET that will obtain by liquid phase polycondensation reaction under nitrogen atmosphere about 210 ℃ of solid state polycondensations 8 hours.The limiting viscosity of the PET of gained is measured in orthomonochlorphenol in 25 ℃, is 0.79dl/g, and density is 1.40g/cm
3The content of glycol ether unit is 0.96% (weight) among this PET.
Then, PET is obtained the square molding product of a staged (stepped square molded product) by injection moulding machine (M-70A is made by Meiki Seisakusho k.k.) in 290 ℃ of moldings.In this molding product, the mist degree (haze) at 4mm thickness place is 5.5%, and the mist degree at 5mm thickness place is 14.3%.The acetaldehyde of the PET square molding product of staged that molding obtains in the time of 275 ℃ is 8ppm.
The PET method preparation identical with embodiment 1 is except following difference: the high purity terephthalic acid who replaces 1,437 weight part with the m-phthalic acid of the high purity terephthalic acid of 1,394 weight part and 43 weight parts; The ANTIMONY TRIOXIDE SB 203 99.8 PCT amount changes 0.46 weight part into; 85% phosphoric acid amount changes 0.20 weight part into.
The limiting viscosity of the PET of gained (liquid phase polycondensation reaction product) is measured in orthomonochlorphenol in 25 ℃, be 0.60dl/g, and PET contains the glycol ether unit of 0.98% (weight).
Then, the identical solid state polycondensation of PET (liquid phase polycondensation reaction product) experience and embodiment 1.The limiting viscosity of the PET of gained is measured in orthomonochlorphenol in 25 ℃, is 0.85dl/g, and density is 1.40g/cm
3, and PET contains the glycol ether unit of 0.98% (weight).
PET uses the method identical with embodiment 1 to be molded as two square molding products of staged.The molding product of making under 290 ℃, the mist degree at 4mm thickness place is 4.2%, the mist degree at 5mm thickness place is 7.5%.The molding product of making under another 275 ℃, its acetaldehyde are 8ppm.
The PET method preparation identical with embodiment 2 is except following difference: 85% phosphoric acid of 0.10 weight part is replaced 85% phosphoric acid of 0.46 weight part and adds second reactor with four hydration cobaltous acetates of 0.24 weight part.
The limiting viscosity of the PET of gained (liquid phase polycondensation reaction product) is measured in orthomonochlorphenol in 25 ℃, is 0.65dl/g, and contains the glycol ether unit of 0.99% (weight).
Then, the identical solid state polycondensation of PET (liquid phase polycondensation reaction product) experience and embodiment 1.The limiting viscosity of the PET of gained is measured in orthomonochlorphenol in 25 ℃, is 0.88dl/g, and density is 1.40g/cm
3, and contain the glycol ether unit of 1.01% (weight).
PET uses the method identical with embodiment 1 to be molded as two square molding products of staged.The molding product of making under 290 ℃, the mist degree at 4mm thickness place is 3.9%, the mist degree at 5mm thickness place is 6.9%.The molding product of making under another 275 ℃, its acetaldehyde are 9ppm.
Embodiment 4
The PET method preparation identical with embodiment 1, except following difference: the amount of ANTIMONY TRIOXIDE SB 203 99.8 PCT changes 0.46 weight part into; Trimethyl phosphite 99 with 0.24 weight part replaces 85% phosphoric acid.
The limiting viscosity of the PET of gained (liquid phase polycondensation reaction product) is measured in orthomonochlorphenol in 25 ℃, be 0.64dl/g, and PET contains the glycol ether unit of 1.02% (weight).
Then, the identical solid state polycondensation of PET (liquid phase polycondensation reaction product) experience and embodiment 1.The limiting viscosity of the PET of gained is measured in orthomonochlorphenol in 25 ℃, is 0.85dl/g, and density is 1.40g/cm
3, and PET contains the glycol ether unit of 1.03% (weight).
PET uses the method identical with embodiment 1 to be molded as two square molding products of staged.The molding product of making under 290 ℃, the mist degree at 4mm thickness place is 6.0%, the mist degree at 5mm thickness place is 13.2%.The molding product of making under another 275 ℃, its acetaldehyde are 10ppm.
The PET method preparation identical with embodiment 3 is except following difference: use the high purity terephthalic acid of 1,365 weight part and the m-phthalic acid of 72 weight parts; The ANTIMONY TRIOXIDE SB 203 99.8 PCT amount changes 0.39 weight part into.
The limiting viscosity of the PET of gained (liquid phase polycondensation reaction product) is measured in orthomonochlorphenol in 25 ℃, be 0.60dl/g, and PET contains the glycol ether unit of 0.92% (weight).
Then, the identical solid state polycondensation of PET (liquid phase polycondensation reaction product) experience and embodiment 1.The limiting viscosity of the PET of gained is measured in orthomonochlorphenol in 25 ℃, is 0.80dl/g, and density is 1.40g/cm
3, and PET contains the glycol ether unit of 0.92% (weight).
PET uses the method identical with embodiment 1 to be molded as two square molding products of staged.The molding product of making under 290 ℃, the mist degree at 4mm thickness place is 3.4%, the mist degree at 5mm thickness place is 4.7%.The molding product of making under another 275 ℃, its acetaldehyde are 10ppm.
Comparing embodiment 1
The PET method preparation identical with embodiment 1, except following difference: ANTIMONY TRIOXIDE SB 203 99.8 PCT adds second reactor rather than first reactor.
The limiting viscosity of the PET of gained (liquid phase polycondensation reaction product) is measured in orthomonochlorphenol in 25 ℃, be 0.57dl/g, and PET contains the glycol ether unit of 0.97% (weight).
Then, the identical solid state polycondensation of PET (liquid phase polycondensation reaction product) experience and embodiment 1.The limiting viscosity of the PET of gained is measured in orthomonochlorphenol in 25 ℃, is 0.80dl/g, and density is 1.40g/cm
3, and PET contains the glycol ether unit of 0.97% (weight).
PET uses the method identical with embodiment 1 to be molded as two square molding products of staged.The molding product of making under 290 ℃, the mist degree at 4mm thickness place is 9.6%, and the mist degree at 5mm thickness place is 35.5%, and these data show poor transparency.The molding product of making under 275 ℃, its acetaldehyde are 7ppm.
Comparing embodiment 2
The PET method preparation identical with embodiment 2, different except not adding this point of phosphoric acid of 85%.
The limiting viscosity of the PET of gained (liquid phase polycondensation reaction product) is measured in orthomonochlorphenol in 25 ℃, be 0.66dl/g, and PET contains the glycol ether unit of 0.95% (weight).
Then, the identical solid state polycondensation of PET (liquid phase polycondensation reaction product) experience and embodiment 1.The limiting viscosity of the PET of gained is measured in orthomonochlorphenol in 25 ℃, is 0.89dl/g, and density is 1.40g/cm
3, and PET contains the glycol ether unit of 0.96% (weight).
PET uses the method identical with embodiment 1 to be molded as two square molding products of staged.The molding product of making under 290 ℃, the mist degree at 4mm thickness place is 4.4%, the mist degree at 5mm thickness place is 8.1%.The molding product of making under 275 ℃, its acetaldehyde are 14ppm, and this is that the high acetaldehyde of used PET causes.
Comparing embodiment 3
The PET method preparation identical with embodiment 2, except following difference: 85% phosphoric acid adds first reactor rather than second reactor.
The limiting viscosity of the PET of gained (liquid phase polycondensation reaction product) is measured in orthomonochlorphenol in 25 ℃, be 0.56dl/g, and PET contains the glycol ether unit of 0.92% (weight).
Then, the identical solid state polycondensation of PET (liquid phase polycondensation reaction product) experience and embodiment 1.The limiting viscosity of the PET of gained is measured in orthomonochlorphenol in 25 ℃, is 0.80dl/g, and density is 1.40g/cm
3, and PET contains the glycol ether unit of 0.95% (weight).
PET uses the method identical with embodiment 1 to be molded as the square molding product of staged.The molding product of 290 ℃ of formation, the mist degree at 4mm thickness place is 10.1%, and the mist degree at 5mm thickness place is 37.2%, and these data show poor transparency.The molding product of 275 ℃ of formation, its acetaldehyde are 10ppm.
Claims (7)
1. method for preparing polyethylene terephthalate, this method is carried out in the polyester manufacture device, this device comprises the esterifier of being made up of a plurality of continuous esterification devices, liquid phase polycondensation reaction device and optional solid state polycondensation device is characterized in that said method comprising the steps of:
The slurries that will contain terephthalic acid, ethylene glycol and antimony compounds add in first esterifier; And
With a kind of phosphorus compound, and optional, be selected from least a compound in cobalt compound, magnesium compound and the manganic compound add second or later esterifier in.
2. the method for preparing polyethylene terephthalate as claimed in claim 1 is characterized in that described antimony compounds is an ANTIMONY TRIOXIDE SB 203 99.8 PCT.
3. the method for preparing polyethylene terephthalate as claimed in claim 1 or 2, the content that it is characterized in that antimony compounds in the described slurries are 150 to 400ppm, in terephthalic acid.
4. the method for preparing polyethylene terephthalate as claimed in claim 1 or 2 is characterized in that the described slurries that contain terephthalic acid, ethylene glycol and antimony compounds are to prepare under 0 to 50 ℃ temperature.
5. the method for preparing polyethylene terephthalate as claimed in claim 1 or 2 is characterized in that temperature of reaction in first esterifier is in 240 to 270 ℃ scope.
6. the method for preparing polyethylene terephthalate as claimed in claim 1 or 2 is characterized in that phosphorus compound, cobalt compound and antimony compounds add with aqueous solution form.
7. the method for preparing polyethylene terephthalate as claimed in claim 1 or 2 is characterized in that except terephthalic acid, uses m-phthalic acid as the dicarboxylic acid component, and its molar content is 1 to 3%, in all dicarboxylic acid components.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24168796A JP3300613B2 (en) | 1996-09-12 | 1996-09-12 | Method for producing polyethylene terephthalate |
| JP241687/1996 | 1996-09-12 | ||
| JP241687/96 | 1996-09-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1176263A CN1176263A (en) | 1998-03-18 |
| CN1147521C true CN1147521C (en) | 2004-04-28 |
Family
ID=17078031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB971182884A Expired - Fee Related CN1147521C (en) | 1996-09-12 | 1997-09-12 | Process for preparing polyethylene terephthalate |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP3300613B2 (en) |
| KR (1) | KR100468794B1 (en) |
| CN (1) | CN1147521C (en) |
| ID (1) | ID19587A (en) |
| TW (1) | TW419491B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4177769B2 (en) * | 2004-02-04 | 2008-11-05 | 株式会社日立製作所 | Polymer synthesizer |
| JP4867421B2 (en) * | 2006-03-24 | 2012-02-01 | 東洋紡績株式会社 | Continuous production method of copolyester |
| KR100764378B1 (en) * | 2006-11-22 | 2007-10-08 | 주식회사 효성 | Manufacturing method of flame retardant polyester polymer, polyester polymer and fiber therefrom |
| CN101302285B (en) * | 2008-06-20 | 2011-11-30 | 中国石化仪征化纤股份有限公司 | production process of polyethylene glycol terephthalate |
| CN104788651B (en) * | 2015-04-29 | 2017-03-29 | 上海天坛助剂有限公司 | A kind of production method of the environment-friendly type sizing material polyester for textile sizing |
| CN111410733A (en) * | 2020-04-26 | 2020-07-14 | 扬州御泓再生资源有限公司 | Processing technology of special material for producing regenerated polyester for chemical fibers |
-
1996
- 1996-09-12 JP JP24168796A patent/JP3300613B2/en not_active Expired - Fee Related
-
1997
- 1997-09-05 TW TW086112845A patent/TW419491B/en not_active IP Right Cessation
- 1997-09-10 ID IDP973138A patent/ID19587A/en unknown
- 1997-09-10 KR KR1019970046512A patent/KR100468794B1/en active IP Right Grant
- 1997-09-12 CN CNB971182884A patent/CN1147521C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| KR100468794B1 (en) | 2005-07-07 |
| JP3300613B2 (en) | 2002-07-08 |
| JPH1087807A (en) | 1998-04-07 |
| CN1176263A (en) | 1998-03-18 |
| KR19980024490A (en) | 1998-07-06 |
| ID19587A (en) | 1998-07-23 |
| TW419491B (en) | 2001-01-21 |
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Applicant after: Mitsui Chemical Industry Co., Ltd. Applicant before: Mitsui Petrochemical Industries, Ltd. |
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Free format text: CORRECT: APPLICANT; FROM: MITSUI SEKIYU K.K.K. TO: MITSUI CHEMICALS, INC. |
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